Process for producing fine silk fibroin powder

Abstract: A method for producing silk fibroin ultrafine powder comprising: a first step for pulverizing silk fibroin into a crushed powder state by means of a dry-type mechanical pulverization means, a second step for pulverizing the silk fibroin crushed powder into a fine powder state by means of a dry-type mechanical pulverization means; a third step for pulverizing the silk fibroin fine powder into a ultrafine powder having average particle diameter on or less than 10µm by means of a dry-type mechanical pulverization means; and a step for beta-treating the silk fibroin powder in at least one step of the first to third steps or after the three steps.

Description: This invention relates to a method for producing a substance including natural organic substance fine powder such as a silk fine powder, and can be used in plastics film or sheet, coating medium, fiber treatment agents and the like. There have been proposed various kinds of methods for producing silk fibroin fine powder such as following (a)-(b) conventional methods. (a) The Japanese Patent Publication No. 39-1941 has proposed a method for producing silk fibroin for chromatograph including steps of dissolving silk fibroin into cupro-ethylenediamine solution, adding alcohols to silk fibroin solution obtained by dialysis, drying deposit, and pulverizing the thus dried deposit. (b) The Japanese Patent Publications No. 61-36840 and 63-51160 have proposed methods for producing silk fibroin including steps of soaking silk thread first of all, pressurizing and heating it in a pressure chamber by means of saturated steam, disposing it abruptly under low pressure to expand, and drying and pulverizing it. (c) The Japanese Patent Laid-open No. 4-300369 has proposed a method having steps of conducting hydrolysis of figure by means of hydrochloric acid for deterioration processing and mechanically pulverizing it. In accordance with the conventional method (a), since the internal structure of silk fibroin is once broken drown in such chemical treatment, the natural drape of silk may be injured. In the conventional method (b), a rather high producing skill will be required since required steps such as heating and pressuring are too complicated. In accordance with the conventional method (c), it has been known that deterioration degree control of silk when conducting deterioration processing by using hydrochloric acid is difficult and the natural drape of silk may not be obtained as in the (a) method. Though a preferable silk fibroin fine powder should be effectively dispresed in resin solution (DMF, MKE, Water, etc) before its application into synthetic leather, simulated synthetic leather substitute, film, sheet and so on, the above-mentioned silk fibroin fine powder could not be done well. If the silk fibroin fine powder can not be dispersed well or aggregates, so called touch feeling gets worse and the drape may be ruined. Various products containing silk fibroin particles, which are obtainable by the prior art methods, may not always be satisfactory in the moisture absorbing/releasing property, sense of touch, appearance, etc. It is the first object of the present invention to provide a method of producing silk fibroin ultrafine powder which has the particle size on or less than 10 µm and disperses well in the products. A second object of the invention is to provide superfine silk fibroin particles which is obtainable by the above method. Regarding paints containing silk fibroin particles, for instance, it has been difficult to obtain paints having pastel colors, white color, light colors, etc., because the silk fibroin particles obtainable by the prior art method is colored to be yellow to green. Further, with data display surface formation paints containing silk fibroin particles, satisfactory moisture absorbing/releasing property as well as writing accepting property and excellent sense of touch based on the moisture absorbing/releasing property may not always be obtained depending on the silk fibroin particles obtained by the prior art method. A third object of the invention is to provide various products containing silk fibroin particles as noted above. According to a first aspect of the present invention, a method for producing silk fibroin ultrafine powder comprises a first step for pulverizing silk fibroin into a crushed powder state by means of a dry-type mechanical pulverization means; a second step for pulverizing the silk fibroin crushed powder into a fine powder state by means of a dry-type mechanical pulverization means; a third step for pulverizing the silk fibroin fine powder into a ultrafine powder having average particle diameter on or less than 10µm by means of a dry-type mechanical pulverization means; and a step for beta-treating the silk fibroin powder in at least one step of said first to thirds steps or after said three steps. The average particle diameter of the crushed powder is recommended to be about 100µm. The average particle diameter of the fine powder is about 20µm. The dry-type mechanical pulverization means used in the first pulverizing step may be any mill such as a rotary blade mill,.but the dry-type mechanical pulverization means used in the second pulverizing step should be a ball mill and the dry-type mechanical pulverization means used in the third pulverizing step should be a jet mill. As there are three steps of pulverization by means of several dry-type mechanical pulverization means to subsequently obtain the powders each having different particle diameter, the most preferable ultrafine powder which can not be produced by only once mechanical pulverization will be constantly produced. The beta treatment done in the method should be understood to soak silk fibroin into a predetermined liquid to increase the beta structure degree. Incidentally, the recommended liquid is for example solvent medium, neutral saline solution or the like. The solvent medium is to be alcohols such as methanol and ethanol, or acetone and so on. The recommended normal salt is for example sodium chloride, potassium chloride, sodium sulfate, ammonium sulfate, sodium nitrate. The beta-treating of the silk fibroin powder should be done in at least one step of the first to thirds steps or after the three steps. Of course, it can be done over 2 times upon reviewing several conditions. Conducting beta treatment, the crystallinity index will increase, preferably more than 70% of natural silk thread whereby the silk fibroin ultrafine powder can be uniformly dispersed in a solvent medium resin solution, water resin solution or the like. As a result, the drape of natural silk can be maintained and the final products has fine moisture absorption and discharge property, moisture permeation property, touch teeling and further shows excellent antistatic properties and anti-blocking performance. The final products are for example simulated synthetic leather substitute, synthetic leather, fiber, rubber, film sheet and fiber. According to a second aspect of the present invention, superfine silk fibroin particles manufactured by a process comprising a first commuting process for commuting silk fibroin into coarse particles with dry mechanical commuting means, a second commuting step of commuting said coarse silk fibroin particles into fine particles with dry mechanical commuting means, said a third commuting means for commuting said fine silk fibroin particles into superfine particles with an average particle diameter of 10µm with dry mechanical commuting means, the silk fibroin particles being beta-treated during or after at least one of said first to third commuting steps. A solvent type resin composition containing superfine silk fibroin particles according to the invention, is obtainable by incorporating the superfine silk fibroin particles in a solvent type resin solution. Typical examples of the solvent type resin solution are polyurethane resins, acrylic resins, polyamide resins, etc. The solvent in the solvent type polyurethane solution may be diethyl formamide, methyl ethyl ketone, toluene, isopropyl alcohol, etc. A film or sheet containing superfine silk fibroid powder is obtainable by incorporating the superfine silk fibroid powder in a solvent type resin solution. The film or sheet noted above may be formed by dry or wet knife coating, graver coating, spraying, dipping, etc. As a lamination process may be used, when using a polyurethane resin, for instance, one in which a base material is impregnated with a resin solution containing the superfine silk fibrin particles, a wet process in which the above solution is coated on the base material to form a film thereon, or a dry process in which a film or sheet containing the superfine silk fibroin particles is formed using the above solution or the like and laminated on the base material either directly or via an adhesive. The thermoplastic resin composition containing superfine silk fibroin particles according to the invention, is obtainable by adding the superfine silk fibroin particles to the thermoplastic resin solution. Typical examples of the thermoplastic resin are chain-like low density polyethylene resin (L-LDPE), polypropylene resin (PP), polystyrene resin (PS), high density polyethylene resin (HDPE), thermoplastic olefin resin (TPD), etc. A film or a sheet containing superfine silk fibroin particles is obtained by incorporating the superfine silk fibroin particles. Depending on purposes, such as quality stabilization, or on environments of use, the film or sheet according to the invention may contain necessary amounts of additives usually used in this field, such as fibers, anti-oxidization agents, ultraviolet radiation absorbers as well as processibility improving agents, e.g., plasticizers, stabilizers, lubricants, etc., fillers, and coloring agents, dies, pigments, etc. The proportions of the superfine silk fibroin particles and the synthetic resin are in a range of 1 to 60wt% of superfine silk fibroin particles for 99 to 10wt% of the synthetic resin solid part. If the proportion of the superfine powder exceeds 60wt%, the film or sheet may be fragile. If the proportion is less than 1wt%, the effects of adding the powder can not be obtained. However, the proportion of the superfine powder in the synthetic resin is suitable 5 to 50wt%. The film or sheet suitably has a thickness of 5µm or above, and the superfine powder is suitably dispersed uniformly. The superfine power may be exposed to the surface. This state is useful for improving the sense of touch or sense of warmness. The film or sheet may be formed by calendar forming, T-die forming, inflation forming, etc. Further, the laminate is formed such that a film or a sheet containing the superfine silk fibroin particles is one of a plurality of layers laminated on a base material or is the base material itself. The base material may be woven cloth of natural or chemical fibers as noted above, cotton cloth, non-woven cloth, synthetic resin films or sheets, leather, paper, etc. If necessary, the laminate may be surface finished by buffing, emboss rolling, etc. As the laminating process may be adopted coating, wet lamination, extrusion lamination, dry lamination, press lamination, stamping, metal fitting, etc. The molding is formed by injection molding, blow molding, hollow molding or press molding a thermoplastic resin composition containing the superfine silk fibroin particles, which is obtained by incorporating the superfine silk fibroin particles in a thermoplastic resin. The superfine powder may be exposed to the surface of the molding. This state is useful for improving the sense of touch or sense of warmness. Further, a composite molding or molding is molded such as to be integral with a different material. The different material may be woven cloth of natural or chemical fibers, cotton cloth, non-woven cloth, synthetic resin moldings, films or sheets, paper, etc. If necessary, the molding may be surface finished by buffing or squeezing. The fiber processing material according to the invention is obtained by incorporating the superfine silk fibroin particles in a resin emulsion. The fiber processing material contains 99 to 10 wt. parts of the resin emulsion as solit part and 1 to 90 wt. parts of the superfine silk fibroin particles. Further, it contains an adequate solvent component, for instance water. For improving the durability, a cross-linking agent (of epoxy type, melamine type, etc.) or a coupling agent may be added to the fiber processing material. Further, for suppressing the precipitation or aggregation of the superfine silk fibroin particles in the fiber processing material bath, usual anti-precipitation agent or dispersing agent may be added. An example of the anti-precipitation agent is a non-ionic active agent derived from fatty acid or high grade alcohol. Examples of the dispersing agent are sodium polystyrene sulfonic acid, solfonic acid type copolymer ammonium salt, etc. The resin emulsion comprises one or more members of the resin emulsion group consisting of polyurethane type resins, polyester type resins, silicon type resins, fluorine type resins and acrylic type resins. The silicon type resins are suitably those which amino or epoxy denatured and capable of being chemically coupled to the OH group, particularly those of net-like coupling type with functional groups at the opposite ends. These resins are excellent in their effect of preventing the falling of superfine silk fibroin particles and adhesion to fibers. The fiber processing material may be used to process fibers, fiber material cloth and fiber material cotton. The fiber material cloth may be woven cloth, braided cloth, non-woven cloth, etc. The fiber material cotton may be internal cotton, such as in bedclothes, pillows, etc., and internal cotton such as in outfits for cold wheater. The process with the fiber processing material may be done on fibers either in the stage of fibers or a stage of fiber material cloth or fiber material cotton obtained by using fibers. The fiber processing material is coated on the fibers or the like by a pad pocess, a spray process, etc. After the coating, the work is dried and then thermally treated. The drying and subsequent thermal treatment have an effect of improving the durability. The falling prevention effect may be further improved by carrying out the process with the processing material containing the superfine powder and the process of drying twice repeatedly (it being possible to carry out the second process with a processing material without superfine powder) and then carrying out the thermal treatment. The paint is obtained by incorporating the superfine silk fibroin particles in the resin. The paint is readily capable of all color development because of satisfactory white degree of the superfine powder. Further, the superfine powder can be readily incorporated in an aqueous resin because of its satisfactory surface wetting property. The resin may be a solvent type resin or an aqueous resin. Examples of the solvent type resin are acrylic resins, urethane resins, alkid resins, aminno resins, etc. These resins may be used alone or in combinations. Examples of the aqueous resin are such emulsions as vinyl acetate type emulsion, acrylic type emulsion, urethane type emulsion, etc. and also water-soluble acrylic acid, water-soluble urethane, water-soluble epoxy, water-soluble alkid, etc. These resins may be used alone or in combinations. The examples of the paint are oily paints, fiber type derivative paints, synthetic resin paints, rubber derivable paints, aqueous paints, etc. Examples of the solvent in the solvent type paint are thinner, dimethyl formamide, methylethyl ketone, toluene, isopropyl alcohol, etc. Depending on the purposes such as quality stabilization and environments of use, to the paint may be added necessary amounts of usual additives used in this field, for instance dispersing agent, anti-rusting agent, cross-linking agent, hardening agent, ultraviolet radiation absorbing agent, as well as such processibility improving agent as plasticizer, stabilizer, film formation agent, etc., fillter, such coloring agents as die, pigment, quality pigment, etc. The proportions of the superfine silk fibroin particles and the resin for paint, are in a range of 90 to 1wt% of superfine silk fibroin particles for 10 to 99wt% of the resin solid part. If the proportion of the superfine powder exceeds 90wt%, the coating film obtained after drying and fixing may become fragile. If the proportion is less than 1wt%, the effect of adding the superfine powder can not be obtained. The superfine powder is suitably dispersed uniformly in the coating film. The superfine powder may be exposed to the surface. This state is useful for improving the sense of touch, sense of warmness and anti-dazzling effect. The paint may be coated on any work of metal, glass, resin, paper, ceramic, wood, etc. As the paint coating process, an adequate one may be selected such as brush coating, blow coating, electrostatic coating, airless coating, powder coating, etc. in dependence on the work to be coated, coating conditions, drying conditions, coating scale, etc. With the paint it is possible to obtain satisfactory moisture absorbing/releasing property, and attachment of fingerprints or other contaminants is less liable. Such paint has an anti-dazzling effect and does not reflect light, and this it is suited for the interior coating of cars and the like. Further, it provides for settled color tone and thus gives a high grade sense. Further, the paint provides for good sense of touch and is thus suited for coating of parts touched by the hands, such as hole electric products and stationaries. The data display surface formation paint is obtained by incorporating the superfine silk fibroin particles in paint components. The paints are roughly classified into those of solvent type and those of aqueous type. The invention is applicable to both types of paints. Main paint components are (1)base resin, (2)solvent, (3)auxiliary agent and (4)pigment. These components are of the following contents. (1) Base resin Typical examples of the base resin are acrylic acid, urethane, vinyl, epoxy, cellulose, chlorinated polyolefin, etc. One or more members of this group is selectively used. Regarding current data display surface formation paints and ordinary paints, those of aqueous type are being developed in view of environment and like problems. As for the data display surface formation paints as well, the resins to be used have to be determined in dependence on the work to be printed, purpose of printing, environment problems and other conditions. (2) Solvent The aqueous paints use various solvents such as those of aliphatic hydrocarbon type, ketone type, alcohol type, aromatic hydrocarbon type, ether type, etc. The solvent to be used is selected in dependence on the kind of resin used, work to be printed, printing process, purpose of printing, etc., and its content is determined in dependence of its kind. (3) Auxiliary agent The auxiliary agent is selected in dependence on the purpose of printing, work to be printed, printing conditions, etc. The purpose of printing may be strengthening of the physical properties of the coating film, improvement of the setting property, etc. (4) Pigment The pigments are usually used to permit discrimination of paints in colors, provide mat tones, etc. The paint according to the invention may contain individual components in desired proportions, for instance as follows. Resin component: 5 to 30% Pigment comonent: 0 to 40% Silk fibroin: 5 to 90% Solvent component: Remainder The paint may be printed on the printing surface of work by a usual printing process, such as screen printing, gravure printing, flexthographic printing, pad printing, etc. The data display surface formation paint can impart the coating film with an excellent moisture absorbing/releasing property because it contains the superfine silk fibroin particles. It is thus possible to write anything by superimposition writing on the coating film with a writing tool. In addition, greatly improved sense of writing is obtainable. Further, the written letters can satisfactorily resist wear. Further, the coating film obtained with the data display surface formation paint has good sense of touch and is thus suited for home electric products, stationaries and other things that are to be touched by people. Further, it has a matting effect, and thus it is possible to obtain high grade sense. in the accompanying drawings:- Fig. 1 is a distribution graph regarding to particle size of the silk fibroin ultrafine powder in accordance with the present invention; Fig. 2 is a schematic view showing a dry coating apparatus used in the embodiment of the invention; Fig. 3 is a schematic view showing a gravure coating apparatus used in the embodiment of the invention; Fig. 4 is a schematic view showing a wet coating apparatus in the embodiment of the invention; and Fig. 5 is a schematic view showing an impregnation coating apparatus in the embodiment of the invention. The following are examples concerning the method of manufacturing superfine silk fibroin particles and the superfine powder obtained by the same method. Example 1 The details of the method of producing silk fibroin ultrafine powder of the preferable embodiment in accordance with the present invention and a film using the produced ultrafine powder. A raw silk is first cut into by from 2 to 3 centimeters by means of a cutting blade mill and is then soaked in just warm water or warm water containing oxygen to be refined to thereby produce silk fibroin material without any sericin. It should be noted that a material of silk fibroin without refining may affect the final powder so as to have poor touch feeling and be colored into lean brown color. The cut silk fibroin is pulverized into silk fibroin crushed powder state having average particle diameter of 100 µm by a rotary blade mill [Orient vertical type pulverizing machine VM-32 (Trademark) produced by ORIENT CO., LTD.] and the silk fibroin crushed powder is fed into a streaming drying machine to be dried at a temperature of 100°C for 6 hours. The temperature for drying process should be at most 130°C, preferably from 90-110°C. Higher temperature over 130°C may cause a change of color. The operating time should be over one hour. A short drying process will severely harm the color of powder when pulverized in a ball mill of which wall is made of stainless making the powder be worn away. However, if the wall of the ball mill is made of another material such as ceramics not harm color of the powder, the above mentioned drying process can be obviated. Incidentally, the particle size of powder is measured by means of a laser rotating type particle-size analyzer [SK LASER PRO 7000S (trademark) made of SEISIN CO., LTD., dispersion medium: ethanol, dispersion condition: supersonic wave 60 seconds]. The silk fibroin crushed powder is further pulverized for 12 hours by means of a ball mill [made of KONDO CHEMICAL MACHINE MANUFACTURE CO., LTD.] to obtain silk fibroin fine powder having average particle diameter of about 20 µm. The used ball mill is defined by a ceramic wall and a ball made of aluminum to prevent color change of the powder. The average particle diameter can be smaller than 20µm by means of the same ball mill, otherwise the powder will be pulverized by a later jet mill. However, in view of working efficiency, the pulverizing process by the ball mill should complete when the average particle diameter reaches at about 20µm. The further pulverization by the ball mill to obtain smaller particles will take much time and does not effect the particle diameter after pulverized in the jet mill. The silk fibroin fine powder in the ball mill is transmitted into a chamber, into which methanol is poured and stirred for one hour in the room temperature to improve crystallinity index as beta treatment. The silk fibroin fine powder is then removed and dried. The beta treatment is necessary for the obtained powder to disperse well in resin solution to produce the goods. This silk fibroin fine powder is pulverized in the jet mill (Single truck jet mill (trademark) produced by SEISHIN CO., LTD.] to become ultrafine powder state having the average particle diameter of 3.252µm. The handled volume of powder in this pulverizing is 5kg/h. Fig. 1 is a distribution graph regarding to particle size of the silk fibroin ultrafine powder in accordance with the present inanition. In the drawing, a curve graph is cumulative sum weight Q 3 and a bar graph is weight frequency q 3 . The silk fibroin ultrafine powder is combined with solvent urethane [Rezamin ME3612LP (trademark) produced by DAI NICHI SEIKA KOGYO CO., LTD.] which is diluted by dimethylformamide/methyl ethyl ketone=1/1 so as to occupy 30wt% by weight against resin solids content and is then applied on peelable pattern paper by using a roll bar by a thickness of 30µm. The solvent medium in applied substance is completely evaporated in a drying operation and then the formed film is peeled off from the peelable pattern paper as a film containing ultrafine powder in accordance with the present invention. The respective films are measured for moisture absorption amount, moisture discharge amount, moisture permeability and frictional electrification voltage and organoleptic evaluations have been also conducted. Those results are shown in Tables 1 and 2. The measurement of moisture discharge amount will be done as follows. 1 ○ Selecting a film to be tested having an even thickness entirely by directly measuring the thickness of the film. 2 ○ Cutting out the film to have an area of 12 square centimeters. 3 ○ Putting the cut film on an aluminum plate similar in size by means of adhesive-backed tapes to expose a part portion thereof having an area of 10 square centimeters. 4 ○The thus-obtained sample is left as it is for at least 12 hours in a first thermostatic and hydrostat chamber in which the temperature is always kept at the temperature of 23°C and the relative humidity (RH) is also kept constantly at the degree of 30%. 5 ○Taking out the sample from the first thermostatic and hydrostat chamber to measure and record the instant weight. 6 ○Putting promptly the sample into a second thermostatic and hydrostat chamber (Temperature=30 °C, Relative humidity=80%). 7 ○Measuring and recording the weight of the sample every one hour for 4 hours. The gap of the measured weight compared with that in 5 ○ can be of moisture absorption amount. 8 ○ Resetting the sample in the first thermostatic and hydrostat chamber, and measuring and recording the weight of the sample every one hour for 4 hours. The gap of the measured weight compared with the fourth measured weight in 7 ○ can be of moisture discharge amount. The moisture permeability is measured conforming to Japanese Industrial Standard (JIS) L-1099. The organoleptic evaluation is evaluated by twenty persons in random who touch the film in this preferable embodiment. The each mark in the table should be considered as the mean value of twenty-person. The marking is conducted out of 5 grades. Mark 5 ··· Excellent touch feeling, Mark 4 ··· Satisfactory touch feeling, Mark 3 ··· Fair touch feeling, Mark 2 ··· Inferior touch feeling, and Mark 1 ··· Worst touch feeling. The frictional electrification voltage is measured confirming to Japanese Industrial Standard (JIS) L-1094B. Another film for a comparative example not containing ultrafine powder in accordance with the preferred embodiment is also prepared and is measured for and evaluated several properties as in the above-mentioned embodiment. The results are shown in the following tables 1 and 2. Absorbed Water(g/m 3 ) Discharged Water(g/m 3 ) 1 hour 2 hour 3 hour 4 hour 1 hour 2 hour 3 hour 4 hour Example 1 4.1 5.9 6.9 8.5 2.8 4.1 4.9 5.8 Com. Example 1 2.8 4.4 5.3 6.3 2.0 3.2 3.8 4.5 Note: Com. Example means Comparative Example Moisture Permeability (mg/m 2 /24hr) Organoleptic evaluation Frictional electrification voltage (v) Example 1 2000 4.2 425 Com. Example 1 1400 2.3 3250 Note: Com. Example means Comparative Example Reviewing the measurement and evaluation results, it can be noted that the film using ultrafine powder produced by the method in accordance with Example 1 is of silk fibroin ultrafine powder after beta treatment by which ultrafine powder is well dispersed in the film, so that the obtained film is fine in moisture absorption and discharge property and antistatic properties and provides conformable touch feeling and further maintains drape of natural silk. On the contrary, however, as the film prepared in the comparative example does not contain silk fibroin ultrafine powder, it is inferior in moisture absorption and discharge property and antistatic properties. The touch feeling is not comfortable, too. The respective crystallinity index of fibroin ultrafine powders A, B, C and natural silk thread are measured, the fibroin ultrafine powders A and B being processed by the beta treatment in the method according to the preferable embodiment and the fibroin ultrafine powder C being processed only without beta treatment. The crystallinity index of the fibroin ultrafine powders A, B, C to natural silk thread is shown in table 3 . The crystallinity index is measured in conformity with X-ray analysis ( Blag angle 2=5° ∼45° ). The dispersion property in respective solvent mediums of A, B, C is evaluated in the following table 3 in which "○" means a fine state, "Δ" means an inferior state, "×" means a condensation state. Crystallinity index against Dispersion property in solvent medium natural silk thread Water DMF MEK MeOH A 81.25 % ○ ○ ○ ○ B 74.30 % ○ ○ ○ ○ C 68.75 % Δ × × Δ Reviewing Table 3, the fibroin ultrafine powder obtained by the method of the preferred embodiment has large crystallinity index to natural silk thread after the beta treatment and shows improved dispersion property in solvent medium. In another Comparative Example, it is tested to produce a film using ultrafine powder which is produced only without the beta treatment as in the above mentioned embodiment, however condensation state of the ultrafine powder comes in sight and disturbs a production of film because the ultrafine powder could not disperse uniformly in the solvent medium resin. Herein under are given examples of solvent type resin composition, film or sheet containing superfine silk fibroin particles and laminate using the same. Example 2 The superfine silk fibroin particles used in this example was obtained in the same way as in Example 1 . 90wt% of the solid part of a polyurethane solution ("Rezamine 3612LP" manufactured by Dainichi Seika Co., Ltd.) and 10wt% of superfine silk fibroin particles were mixed to obtain a blend resin solution (with 20wt% of solid part), which was coated on separable paper using a coater and then dried at 70°C to form a film with a thickness of 30µm. Example 3 A film was produced in the same way as in Example 2. except for that 30wt% of superfine silk fibroin particles was mixed with 70wt% of the polyurethane solution. Example 4 A film was produced in the same way as in Example 2 except for that 50wt% of polyurethane solution solid part and 50wt% of superfine silk fibroin particles were mixed. Example 5 A coating solution (i.e., a solution prepared by adding slight amounts of additives to a dry polyurethane resin solution obtained by incorporating 6wt% of superfine silk fibroin particles) 12 was coated on a separable paper sheet 11 using a dry coating apparatus as shown in Fig. 2, and then dried using a drier 13 at 130°C to produce a polyurethane film 14 with a thickness of 20µm and containing superfine silk fibroin particles. Then, the film 14 was bonded to a base material 16 constituted by non-woven cloth of polyester of one denier and weighing 70g/m 2 by using an adhesive (i.e., a polyurethane adhesive containing 5wt% of superfine silk fibroin particles on the solid part basis) 15, followed by drying at 140°C using a drier 17 to produce a synthetic leather 18 having a polyurethane resin layer 40µm thick and containing superfine silk fibroin particles. Then, a coating solution (i.e., a polyurethane resin solution containing 5wt% of superfine silk fibroin particles on the solid part basis) 12A was coated on the surface of the synthetic leather 18 and then dried using a drier 13A. Example 6 A coating solution (i.e., a solution obtained by adding a small amount of a filler to a wet polyurethane resin solution containing 30wt% of superfine silk fibroin particles on the solid part basis) 22 was coated on a base material 21 constituted by a woven cloth of blend spun fibers of 50% nylon and 50% tetron using a wet coating apparatus as shown in Fig. 4. The base material 21 is then passed continuously through solidifying/water washing vessels 23A to 23C and then dried using a drier 24 at 140°C to produce a synthetic leather 25 having an ester type polyurethane resin layer with a thickness of 0.70mm and containing superfine silk febroin powder. Then, a coating solution (i.e., a polyurethane resin solution containing 30wt% of superfine silk fibroin particles in the solid part basis) was coated by spray coating on the synthetic leather 25. Example 7 An impregnation coating apparatus as shown in Fig. 5 was used. A base material 31 constituted by non-woven polyester cloth of 2 denier and weighing 70g/m 2 was introduced into an impregnation vessel 32 for impregnation with 30g/m 2 by dry weight an impregnating solution (i.e., a solution obtained by adding 3wt. parts of a filler to an ester type polyurethane resin solution (with 15wt% of solid resin part) containing 25wt% of superfine silk fibroin particles on the solid part basis) 33. Then, the base material 31 is passed through a solidifying/water washing vessel 34 and then dried using a drier 35 at 130°C to obtain an impregnated base material 36. Then, using the impregnation coating apparatus as shown in Fig. 5, the impregnated base material 36 was coated with a coating solution (i.e., a solution obtained by adding a filler and a foaming agent to an ester type polyurethane resin solution (with 15 wt. % of solid resin part) containing 30 wt. % of superfine silk fibroin on the solid part basis) and then introduced into solidifying/water washing vessels 23A to 23C, followed by drying using a drier 24 at 130°C. Thus, an artificial leather was obtained which had a porous polyurethane resin layer with a thickness of 0.4mm. Comparative Example 2 A film was produced in the same way as in Example 2 except for that the superfine silk fibroin particles according to the invention was not used. Comparative Examples 3 to 5 In comparative Examples 3 to 5 a sheet, a synthetic leather and an artificial leather were produced in the same ways as in Examples 5 to 7, respectively, except for that the superfine silk fibroin particles according to the invention was not used. Then, with the film, sheet. svnthetic leather and artificial leather in Examples 5 to 7 and Comparative Examples 2 to 5, the moisture permeability, absorbed moisture amount, released moisture amount or sense of surface touch was tested. The results are shown in Tables 4 and 5 The tests were conducted by the following methods. The absorbed moisture amount was determined by measuring the weight increase of sample by holding one side thereof (i.e., either side in case of single layer sample but the side opposite the base material in case of sample comprising two or more layers) in an atmosphere at 23°C and with 80% RH, the sample having reached the equilibrium at 23°C and with 30% RH. The released moisture amount was determined by measuring the weight reduction of sample by holding one side thereof (the measurement side being the same as in the case of the absorbed moisture amount) in an atmosphere at 23°C and with 30% RH, the sample having reached the equilibrium at 23°C and with 80% RH. The moisture permeability and the surface touch sense were measured in the same ways as in Example 1 . Superfine silk fibroin (wt%) Moisture permeability (g/m 2 24 hrs.) Absorbed moisture (g/m2) Surface touch sense 2 hrs. Example 2 10 1200 0.4 3.85 Com. Ex. 2 0 900 0.2 2.80 Example 3 30 1700 0.7 4.45 Example 4 50 2900 0.9 4.70 Superfine silk fibroin (wt%) Absorbed moisture amount (g/m 2 ) Released moisture amount (g/m 2 ) 20 min. 1 hr. 24 hrs. 20 min. 1 hr. 24 hrs. Example 5 6 2.2 3.6 5.0 2.0 3.0 4.3 Com. Ex. 3 0 0.8 1.2 2.3 0.8 1.2 1.8 Example 6 30 12.0 15.5 22.0 10.5 16.0 22.0 Com. Ex. 4 0 8.2 10.4 12.0 7.0 9.0 11.5 Example 7 25, 30 8.5 10.0 13.0 7.8 9.8 13.0 Com. Ex. 5 0, 0 3.2 4.0 5.5 3.0 4.0 5.4 From Tables 4 and 5, it will be seen that the film, sheet, synthetic leather and artificial leather in Examples 2 to 7 have satisfactory characteristics such as moisture permeability, moisture absorption, moisture releasing and surface touch sense because they contain superfine silk fibroin particles according to the invention. On the other hand, the film, sheet, synthetic leather and artificial leather in Comparative Examples 2 to 5, as seen from Tables 4 and 5, have unsatisfactory characteristics such as moisture permeability, moisture absorption, moisture releasing and surface touch sense because they do not contain superfine silk fibroin according to the invention. Herein under are given examples of thermoplastic resin composition, film and sheet containing superfine silk fibroin particles and laminate using the same. Example 8 The superfine silk fibroin particles used in this example was obtained in the same way as in Example 1. Using a hot air drier, thermoplastic polyurethane ("Estoran C85A11FG", a trade name, manufactured by Takeda Bardish Urethane Industries, Inc.) was dried at 105°C for 4 hours, and superfine silk fibroin particles was dried at 120°C for 6 hours. Then, 69.3wt% of the dried thermoplastic polyurethane, 30wt% of the dried superfine silk fibroin particles and 0.7wt% of phenol type anti-oxidization agent as thermal stabilizer were mixed, and the mixture was kneaded using a two-axis extruder to produce a master batch. The master batch was then dried at 135°C for 6 hours, and then it was mixed with the thermoplastic polyurethane. The superfine silk fibroin particles was incorporated by 10wt%. The material was then dried using a drier with a hopper at 135°C and supplied to an inflation apparatus to produce the thermoplastic polyurethane film (with a thickness of 30µm) in this Example. In this process of manufacture, anti-blocking property during the film formation was checked. The result is shown in Table 6. The anti-blocking property was evaluated in terms of the easiness of separating the inflation molded cylindrical film when the film was opened. As the evaluation standards, the circle mark represents "satisfactory anti-blocking property", the triangle mark represents "usual", and the cross mark represents "unsatisfactory anti-blocking property". With this thermoplastic polyurethane film containing superfine silk fibroin particles, the overall character was evaluated. Also, the moisture permeability, condensation amount and moisture absorption and releasing amounts were measured. The results are shown in Table 7. The overall character was evaluated from the touch, such as sense of touch and softness, by randomly selected ten persons. As the evaluation standards, the double circle mark represents "very good", the circle mark represents "good", the triangle mark represents "usual", and the cross mark represents "bad". The condensation amount was measured in the following way. First, the test room atmosphere was held under conditions of 23°C and 50% RH. In this test room, filter paper impregnated with water was held on a hot plate to cause steam generation. Above the hot plate a sample with dimensions of 10 x 10 cm was held for condensation. The test was conducted in a sealed system lest steam between the filter paper and the sample should escape. After the lapse of 10 minutes, the sample was taken out. Sucking paper was caused to suck water of condensation, and the condensation amount was measured from the weight change. The moisture permeability and moisture absorption and releasing were measured in the same ways as in Example 1. Examples 9 and 10 A thermoplastic polyurethane film containing superfine silk fibroin particles was produced in the same way as in Example 8 except for changing superfine silk powder content. In Example 9, the content was set to 3wt%, and in Example 10 it was set to 6wt%. As in Example 8, the anti-blocking property during the film formation was examined. The result is shown in Table 6. Comparative Examples 6 and 7 In Comparative Example 6, a thermoplastic polyurethane film was produced in the same way as in Example 8 except for that the thermoplastic polyurethane was dried at 105°C for 4 hours and that 3wt% of wax was added as the anti-blocking agent in lieu of the superfine silk fibroin particles. In Comparative Example 7, a thermoplastic polyurethane film was produced in the same way as in Comparative Example 6 except for that no was added. In Comparative Example 6, as in Example 8, the anti-blocking property and the overall character were evaluated. In Comparative Example 7, the sole anti-blocking property was evaluated. The results are shown in Tables 6 and 7. Example 11 A laminate which has a film containing superfine silk fibroin particles as one layer, was produced by bonding the film obtained in Example 8 to a base material constituted by woven cloth of blend spun fibers of 50% nylon and 50% tetron by using an urethane type adhesive for dry laminates. Comparative Example 8 A laminate was produced in the manner as in Example 11 using the polyurethane film produced in Comparative Example 6. With the laminates in Example 11 and Comparative Example 8, as in Example 8, the overall character evaluation and measurements of the moisture absorption and releasing were made. Example 8 Example 9 Example 10 Com. Ex. 6 Com. Ex. 7 Anti-blocking property ○ Δ ○∼Δ ○∼Δ × Examples 8 Example 9 Com. Ex. 6 Com. Ex. 8 Overall character o ○ o ○ Δ Δ Moisture permeability (g/m 2 /24hrs) 1700 - 1200 - Condensation (g/m 2 ) 6.6 - 9.3 - Condensation (g/m 2 ) after 20 min. 1.0 13.0 0.3 8.0 after 1 hr. 1.3 15.3 0.4 10.0 after 4 hrs. 1.5 22.0 0.7 12.0 Releasing (g/m 2 ) after 20 min. 0.9 12.1 0.3 9.0 after 1 hr. 1.2 15.0 0.4 9.0 after 4 hrs. 1.4 21.9 0.6 11.5 From Table 6 and 7, it will be seen that the thermoplastic polyurethane film in Example 8 is excellent in the anti-blocking property and also in the overall character, moisture permeability, anti-condensation property and moisture absorbing/releasing property because it contains the superfine silk fibroin particles according to the invention. As in Examples 9 and 10, however, with less superfine silk fibroin content compared to that in Example 8 the anti-blocking property is correspondingly inferior. The superfine silk fibroin powder thus is to be added in a necessary amount corresponding to the desired characteristic. Further, the laminate in Example 11 which has the thermoplastic polyurethane film as one of a plurality of layers, is excellent in the overall character, moisture absorbing/releasing property, etc. because the thermoplastic polyurethane film contains the superfine silk fibroin film according to the invention. On the other hand, with the thermoplastic polyurethane film in Comparative Example 6, it will be seen that the overall character, moisture absorbing/releasing property, etc. are not so satisfactory as in the example because the anti-blocking agent is a wax. Further, it will be seen that the thermoplastic polyurethane film in Comparative Example 7 has problems in the anti-blocking property because no anti-blocking agent is added. With the laminate in Comparative Example 8 which has the thermoplastic polyurethane film as one of a plurality of layers, the overall character, moisture absorbing/releasing property, etc. are not so satisfactory as in the example because the thermoplastic polyurethane film does not contain the superfine silk fibroin particles according to the invention. A thermoplastic polyurethane film was produced which contained superfine silk fibroin particles without being subjected to the methanol treatment (i.e., beta-treatment). It was found that the superfine silk fibroin particles was dispersed in the film unsatisfactorily. In addition, the moisture absorbing/releasing property of the film was inferior. Herein under are given examples of the molding and composite molding of thermoplastic resin composition containing superfine silk fibroin particles. Example 12 The superfine silk fibroin particles used in this example was obtained in the same way as in Example 1. 90wt% of chain-like low density polyethylene (L-LDPE manufactured by Idemitu Sekiyu Kagaku Co., Ltd.) as thermoplastic resin and 10wt% of superfine silk fibroin particles (with an average particle diameter of 5µm) were mixed, and the mixture was then kneaded using a Bumbury's mixer ("Lavoplast Mill", a trade name, Model B-600, manufactured by Toyo Seiki Seisakusho Co., Ltd.). Then, gas purging was made repeatedly ten times under pressure ranging from 0 to 30kg/cm 2 a press molder (i.e., an oil hydraulic molder for thermal fusion molding Model HT-50-C, manufactured by KitaJuji Co., Ltd.), followed by molding under conditions of 100kg/cm 2 , 160°C and 3 minutes and then cooling under 100kg/cm 2 for 10 minutes using the same press molder (for cooling), thus obtaining a thermoplastic resin composition molding containing superfine silk fibroin particles. The molding temperature was 160°C in case of L-LDPE and TPO and 200°C in case of PS and HDPE. Example 13 A thermoplastic resin composition molding containing superfine silk fibroin particles was obtained in the same way as in Example 12 except for that the content of L-LDPE was set to 60wt% and the content of the superfine silk fibroin particles to 40wt%. Examples 14 and 15 In these examples, molding products were obtained in the same way as in Example 12 except for that thermoplastic polyolefin elastomer (TPO) was used in lieu of L-LDPE. In Example 14, the contents of the TPO and superfine silk fibroin particles were set to 90 and 10wt%, respectively, and in Example 15 the contents of TPO and superfine silk fibroin particles were set to 60 and 40wt%, respectively. Examples 16 and 17 In these examples, molding products were obtained in the same way as in Example 12 except for that polystyrene (PS) was used in lieu of L-LDPE. In Example 16, the contents of the PS and superfine silk fibroin particles were set to 90 and 10wt%, respectively, and in Example 17 the contents of the PS and superfine silk fibroin particles were set to 60 and 40wt%, respectively. Examples 18 and 19 In these examples, molding products were obtained in the same way as in Example 12 except for that high density polyethylene (HDPE) was used in lieu of L-LDPE. In Example 18, the contents of the HDPE and superfine silk fibroin particles were set to 90 to 10 wt%, respectively, and in Example 19 the contents of the HDPE and superfine silk fibroin particles were set to 60 and 40wt%, respectively. Comparative Example 9 A thermoplastic resin composition molding was obtained in the same way as in Example 12 except for that the content of the L-LDPE was set to 100wt% without incorporation of superfine silk fibroin particles. Comparative Example 10 A thermoplastic resin composition molding containing superfine silk fibroin particles was obtained in the same way as in Example 12 except for that the content of the TPO was set to 100wt% without incorporation of superfine silk fibroin particles. Comparative Example 11 A thermoplastic resin composition molding containing superfine silk fibroin particles was obtained in the same way as in Example 12 except for that the HDPE content was set to 100wt% without incorporation of superfine silk fibroin particles. With the moldings in Examples 12 to 19 and Comparative Examples 9 to 12, the moisture absorbing/releasing property, static friction coefficient, and condensation amount were measured, and also the sense of touch, moldability and appearance were evaluated. The results are shown in Table 8. In the Table, F in "F content" means superfine silk fibroin particles. The characteristic measurements and the evaluation were made in the following ways. Moisture absorbing/releasing property In this property, the moisture absorbing property is determined by holding the molding in an atmosphere at 23°C and with a relative humidity of 80% for moisture absorption for 24 hours and then measuring the resultant weight change per unit volume. The moisture releasing property was determined by subsequently holding the molding in an atmosphere at 23°C and with a relative humidity of 30% for moisture releasing for 24 hours and then measuring the resultant weight change per unit volume. Static friction coefficient Idemitsu process was used. Using a compression molded square sheet 2mm in thickness and 10cm in one side, the static friction coefficient was measured with a fiction measuring apparatus (Model AN, manufactured by Toyo Seiki Seisakusho Co., Ltd.). Condensation amount A compression molded square sheet 2mm in thickness and 10cm in one side was used. Filter paper wetted with water was held to be 5 mm blow the underside of the sheet noted above, and the filter paper side was sealed to be at 33°C and with a relative humidity of 100%. Then, the upper surface of the sheet was exposed for 10 minutes to a state at 23°C and with a relative humidity of 50%. Then, the weight of the condensed moisture per unit area was determined by measuring by measuring the amount of water resulting from the condensation on the filter paper side. Sense of touch Moldings for evaluating the sense of touch were produced by using an injection molder ("Toshiba IS-150E" manufactured by Toshiba Co., Ltd.), at a molding temperature of 160°C and a die temperature of 30°C in case of L-LDPE as resin, at a molding temperature of 180°C and a die temperature of 30°C in case of TPO as resin, and at a molding temperature of 200°C and a die temperature of 45°C in case of PS as resin. In case of HDPE as resin, the molding was produced using a flow molder (manufactured by Plako Co., Ltd.) at a molding temperature of 190°C and a die temperature of 30°C. Where the resin used was L-LDPE, TPO (thermoplastic polyolefin elastomer) and PS (polystyrene), the molding that was produced for the touch sense evaluation, was a glasses case (with a length of 18cm, a width of 7 cm, a total width of 14.5cm when the case was open, and a thickness, of 2mm) obtained by injection molding. Where the resin used was HDPE (high density polyethylene), the molding was a bottle (with an outer diameter of 8cm and a height of 17cm) obtained by hollow molding. The touch sense evaluation standards were as follows. 5 points --- "very good sense of touch" 4 points --- "good sense of touch" 3 points --- "usual" 2 points --- "bad sense of touch" 1 point --- "very bad sense of touch" Molding property, Appearance The appearance was evaluated as matting effect. As the molding property, the molding property of the base material was compared under the following conditions. The standards of evaluation of the molding property and appearance were: 3 points --- "good", 2 points --- "usual", 1 point --- "bad". The composite molding according to the invention was obtained by incorporating cotton cloth as internal fitting in the glasses case noted above. Resin (content in wt%) F content (wt%) Moisture absorbin g/releas ing (kg/m3) Static fricti on Conden sation amount (kg/m2 ) Sense of touch Molding proper ty Appear ance E 12 L-LDPE(90) 10 2.7/1.0 0.53 6.8 4 3 2 X 13 L-LDPE(60) 40 9.5/5.7 0.31 2.1 5 3 3 A 14 TPO(90) 10 2.5/1.7 0.66 3.6 4 3 2 M 15 TPO(60) 40 9.4/4.3 0.41 2.7 4 3 3 P 16 PS(90) 10 3.1/1.3 0.31 6.2 5 3 2 L 17 PS(60) 40 12.3/7.1 0.14 5.3 5 2 3 E 18 HDPE(90) 10 2.7/1.1 0.24 6.3 4 2 2 3 S 19 HDPE(60) 40 10.7/4.1 0.23 5.4 5 2 3 From Table 8, it will be seen that the thermoplastic resin composition moldings in Examples 12 to 19 are satisfactory in their moisture absorbing/releasing property, static friction coefficient and condensation amount and, in addition, excellent in the sense of touch, molding property and appearance, because they contain the superfine silk fibroin particles according to the invention. Further, by comparing the superfine silk fibroin particles contents of 10 and 40wt%, with the content of 40wt% the characteristics are generally better. Further, it will be seen that the thermoplastic resin composition moldings in Comparative Examples 9 to 12, unlike those in Examples 12 to 19. are unsatisfactory in the moisture absorbing/releasing property, static friction coefficient and condensation amount and also inferior in the sense of touch, molding property and appearance, because they do not contain the superfine silk fibroin powder according to the invention. Are given examples of the fiber treating material as well as fibers, fiber material cloth and fiber material surface treated with the same fiber treating material. Example 20 The superfine silk fibroin particles used in this example was obtained in the same way as in Example 1. 3g of a reactive amino-denatured silicon type resin emulsion ("Quinset PSR-10", a trade name, with solid part of 30%, manufactured by Kotani Kagaku Co., Ltd.), 3g of the superfine silk fibroin particles and water were mixed such that the total amount was 100ml, thus preparing the fiber treating solution in this example. Then, a polyester cloth for blouses was dipped in this solution. Then, excess treatment material was removed from the cloth with a mangle (with an inter-roll pressure of 1kg/cm 2 ) (pad process). The mangle is a squeezing apparatus comprising a pair of opposed rolls, one being a metal roll and the other being a rubber roll, an wet object being passed through the two rolls to squeeze out water. The resultant cloth was dried at 80°C for 5 minutes. Subsequently, the cloth was heat treated at 170°C for 2 minutes, thus obtaining the fiber material cloth treated with the fiber treating material in this example. Example 21 The same operation was performed as in Example 20 up to the drying step. Then, the cloth was dipped in a bath obtained by adding water to 3g of "Quinset PSR-10" (a trade name) such that the total amount was 100ml. Then, as in Example 20, the work was passed through the mangle, followed by drying and subsequent heat treatment. Examples 22 and 23 In these examples, fiber material cloth samples treated with fiber treating material were obtained in the same way as in Example 20 except for that stocking material cloth was used which was a braiding of composite fibers comprising nylon fibers covering polyurethane core fibers. In Example 23, the same treatment as in Example 21 carried out twice. Examples 24 and 25 In these examples, fiber material cloth samples were obtained in the same way as in Example 20 except for using cotton fabric (broad cloth) for shirts. In Example 25, the same treatment as in Example 21 was carried out twice. Examples 26 and 27 In these examples, fiber material cloth samples treated with fiber treating material were obtained in the same way as in Example 20 except for using an urethane type resin emulsion ("Eslatron S-24", a trade name, with solid part of 45%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in lieu of silicon type resin emulsion and using the same stocking material cloth as in Example 22 in lieu of the polyester material cloth for blouses. In Example 27, the case treatment as in Example 21 was carried out twice. Comparative Example 13 In this comparative example, a fiber material cloth sample was obtained in the same way as in Example 20 except for that the superfine silk fibroin particles was not incorporated. Comparative Example 14 In this comparative example, a fiber material clcth sample was obtained in the same way as in Example 22 except for that the superfine silk fibroin particles was not incorporated. Comparative Example 15 In this comparative example, a fiber material cloth sample was obtained in the same way as in Example 24 except for that the superfine silk fibroin particles was not incorporated. Comparative Example 16 In this comparative example, a fiber material cloth sample was obtained in the same way as in Example 26 except for that the superfine silk fibroin particles was not incorporated. Evaluation of moisture permeability, surface touch sense and washing resistance With the fiber cloth samples obtained in Examples 20 to 27 and Comparative Examples 13 to 16, the moisture absorption property, surface touch sense and washing resistance were evaluated. The results are shown in Table 9. The tests were done in the following ways. (Moisture absorption property) A sample which has reached the equilibrium at 23°C and with 30%, was held in an atmosphere at 23°C and with 80% RH for 4 hours, and the resultant weight increase was measured. (Surface touch sense) The sense of touch on the sample surface with hand was compared. The evaluation was done by 20 randomly selected persons with the following standards (given as average points). 5 points---"very good sense of touch", 4 points---"good sense of touch", 3 points---"usual", 2 points---"bad sense of touch", 1 point---"very bad sense of touch". (Washing resistance) The samples were washed ten times repeatedly using a totally automatic home washer, and the extent of attachment of superfine silk fibroin particles was determined by measuring weights before and after the washing. Moisture absorption (mg/g) Surface touch Washing resistance Weight of cloth (g) Amount of attachment after treatment (g) Percentage of attachment after washing (%) Example 20 - 4.3 6.272 0.195 75.8 Example 21 - 4.2 5.805 0.230 96.2 Example 22 41 4.8 2.246 0.068 80.3 Example 23 38 4.8 2.534 0.072 97.4 Example 24 - 4.2 4.775 0.074 76.2 Example 25 - 4.0 4.767 0.098 91.3 Example 26 42 4.8 2.356 0.064 81.3 Example 27 40 4.8 2.104 0.071 92.5 Com. Ex. 13 - 3.8 6.370 0.093 96.8 Com. Ex. 14 23 4.0 2.301 0.055 98.6 Com. Ex. 15 - 3.2 5.189 0.049 95.7 Com. Ex. 16 28 3.9 2.219 0.044 95.3 From Table 9, it will be seen that the fiber material cloth samples obtained in Examples 20 to 27 are excellent in the moisture absorption property and surface touch sense, because they have been treated with fiber treating material containing the superfine silk fibroin particles according to the invention. Further, the fiber material cloth samples having been treated twice as in Examples 21, 23, 25 and 27, are substantially the same in the per cent attachment after washing as those having been treated with treating material free from superfine silk fibroin particles (Comparative Examples 13 to 16). Thus, it will be seen that with twofold treatment it is possible to improve the falling of superfine silk fibroin particles. On the other hand, it will be seen that the fiber material cloth samples in Comparative Examples 13 to 16 are inferior in the moisture absorbing/releasing property and surface touch sense to the examples, because they have been treated with fiber treating material free from the superfine silk fibroin particles according to the invention. Example 28 This example concerns a fiber treading material solution, which was prepared by mixing 45 and 15 wt. parts, respectively, of "Boncoat AN198" and "Boncoat AN865" (trade names, manufactured by Dainihon Inki Kagaku Co., Ltd.), 1.2 wt. parts of a cross-linking material "CR52" (a trade name, manufactured by Dainihon Inki Kagaku Co., Ltd.), 20 wt. parts of superfine silk fibroin particles and 40 wt. parts of water. The solution was coated by spray coating on polyester inner cotton for ski wear weighing 69g/m 2 , followed by drying at 140°C for 5 minutes, thus obtaining fiber material cotton treated with the fiber treating material in this embodiment. This fiber material cotton weighed 80g/m 2 . Comparative Example 17 In this comparative example, fiber material cotton was obtained in the same way as in Example 28 except for that no superfine silk fibroin particles was added. Evaluation of moisture absorption and anti-charging effect With the fiber material cotton samples obtained in Example 28 and Comparative Example 17, the moisture absorption and anti-charging effect were evaluated. The results are shown in Table 10. (Anti-charging effect) Frictional breakdown voltage was measured in conformity to the JIS L 1094 B process. Absorption (mg/g) Friction breakdown voltage (V) Example 28 20.8 820 Com. Ex. 17 10.2 8300 From Table 10, it will be seen that the fiber material cotton in Example is excellent in the moisture absorbing property and also in the anti-charging effect, because it has been treated with a fiber treating material containing the superfine silk fibroin particles according to the invention. On the other hand, it will be seen that the fiber material cotton in Comparative Example 17 is inferior in the moisture absorbing property and anti-charging effect to the above example, because it has been treated with a fiber treating material free from the superfine silk fibroin particles according to the invention. Herein under are given examples concerning paint containing superfine silk fibroin particles. Example 29 The superfine silk fibroin particles used in this example was obtained in the same way as in Example 1. The paint in this example was prepared by incorporating 10% of the superfine silk fibroin particles in a solvent type urethane resin solution. This paint was then coated by blowing on an ABS sheet (2mm thickness) using a spray gun (manufactured by Iwata Tsoki Kogyo Co., Ltd.). Example 30 Coating was made in the same way as in Example 29 except for that an aqueous urethane resin emulsion ("Superflex 410", a trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used in lieu of the solvent type urethane resin solution. Example 31 This example was the same as Example 29 except for that an iron sheet (2mm thickness) was used as the workpiece to be coated. Comparative Example 18 This comparative example was the same as Example 29 except for that no silk fibroin particles was incorporated in the resin. Comparative Example 19 A paint was prepared in the same way as in Example 29 except for that 10% of fine silica powder was incorporated in lieu of superfine silk fibroin particles. The paint was then coated in the same way as in Example 29. Comparative Example 20 This comparative example was the same as Example 30 except for that no superfine silk fibroin particles was incorporated in the resin. Comparative Example 21 A paint was prepared in the same way as in Example 30 except for that 10% of fine silica powder was incorporated in lieu of superfine silk fibroin particles. The paint was coated in the same way as in Example 29. Comparative Example 22 This Comparative Example was the same as Example 31 except for that an iron sheet (2mm thickness) was used as the workpiece to be coated. Evaluation of the moisture absorption property, touch sense, anti-dazzling property and anti-charging property of paint With the paints in Examples 29 to 31 and Comparative Examples 18 to 22, the moisture absorbing property, touch sense, anti-dazzling property and anti-charging property were evaluated as follows. The results are shown in Table 11. (1)Method of moisture absorption property evaluation Water was coated on the coating film for an area with a width of 2cm and a length of 3cm using a brush, and the time of drying was measured visually. (2)Method of touch sense evaluation 20 randomly selected persons touched the coating film and evaluated the sense of touch to be "excellent", "good" or "bad". (3)Method of anti-dazzling property evaluation A sample was placed on a desk, and it was illuminated with intense light from one side of the desk to the other side. A person who was seated on the other side of the desk checked whether light reflected from the sample was dazzling. 20 persons participated in the evaluation. As the light source was used a reflection lamp for delight color (500W, manufactured by Matsushita Denki Sangyo Co., Ltd.). In Table 22, the circle mark represents "not dazzling", and the cross mark represents "dazzling". (4) Method of anti-charging property evaluation The sample was rubbed with cotton cloth in conformity to JIS-L1094B, and voltage of charging was measured after one minute. The voltage of charging was measured by using a rotary static tester ("Model RST-201, manufactured by Kowa Shokai Co., Ltd.). Moisture absorption (sec.) Touch sense Anti-dazzling property (V) Charging voltage (V) Example 29 13 Excellent ○ 1200 Example 30 10 Excellent ○ 1400 Example 31 14 Excellent ○ 1000 Com. Ex. 18 60 or more Bad × 6000 Com. Ex. 19 42 Bad ○ 5200 Com. Ex. 20 60 or more Bad × 6500 Com. Ex. 21 37 Bad ○ 4800 Com. Ex. 22 40 Bad × 3000 From Table 11, it will be seen that the paints in Examples 29 to 31 are excellent in the moisture absorption property and touch sense, because they contain the superfine silk fibroin particles according to the invention. They are also excellent in the anti-dazzling property and anti-charging property. Particularly, the anti-charging capability is one-third or below of the Comparative Example. On the other hand, it will be seen that the paints in Comparative Examples 18, 20 and 22 are inferior in the moisture absorbing property and touch sense, because they do not contain the superfine silk fibroin particles according to the invention. Further, they are inferior in the anti-dazzling property and anti-charging property. Further, it will be seen that the paints in Comparative Examples 19 and 21 are inferior in the moisture absorption property and touch sense to the paints in the examples, because they contain fine silica powder in lieu of the superfine silk fibroin particles according to the invention. Further, their anti-charging property is unsatisfactory although they pose no problem insofar as the anti-dazzling property is concerned. Herein under are given examples of data display surface formation paint containing superfine silk fibroin particles. Example 32 The superfine silk fibroin particles that was used in this example, was obtained in the same way as in Example 1. In this example, a data display surface formation paint was prepared by adding 15% of the superfine silk fibroin particles obtained in the above way to commercially available solvent type paint "Sericall Ink" (a trade name, manufactured by Teikoku Ink Seizo Co., Ltd.). Example 33 In this example, a data display surface formation paint was prepared by adding 30% of the superfine silk fibroin particles obtained in the above way to an aqueous acrylic emulsion. Comparative Example 23 This comparative example concerns "Sericall Ink" (a trade name) itself. Comparative Example 24 In this comparative example, a data display surface formation paint was prepared by adding 15% of fine silica powder as comparative powder to "Sericall Ink" (a trade name). Comparative Example 25 This comparative example concerns the aqueous acrylic emulsion itself. Comparative Example 26 In this comparative example, a data display surface formation paint was prepared by adding 30% of fine hydrophilic silica powder to an aqueous acrylic emulsion. Evaluation of characteristics The data display surface formation paints in the above examples and comparative examples were each printed on a polycarbonate sheet (with a thickness of 0.5mm) and also on paper for dry PPC "My Paper" (a trade name, manufactured by Nihon Business Supply Co., Ltd.) to obtain samples, and the close contactness, printing property and touch sense of these samples were evaluation. (1)Close contactness The close contactness evaluation test was conducted by applying a wear resistance test. Specifically, 100g of a load was applied to a friction element (i.e., a sheet-like member) provided with "Kanakin No. 3" (a trade name of cotton cloth) and rubbing the sample surface 50 times with this friction element. It was found that the samples in Examples 32 and 33 and Comparative Examples 23 to 26 were all satisfactory in the close contactness of the data display surface formation paint. (2) Printing property The printing property evaluation test was conducted by making screen printing on each sample, and observing the printing property. It was found that the samples in Examples 32 and 33 and Comparative Examples 23 to 26 were all satisfactory in the printing property. (3) Writing accessibility Superimposition writing is made on each sample by using the following writing tools. The evaluation was made by measuring the time until the superimposition written letters were dried. The measurement was made four or more times. The results are shown in Table 12. Time until drying of paint(sec.) Writing tool(1) Writing tool (2) Writing tool (3) Writing tool (3) Example 32 5.6 7.4 3 or less 4.7 Example 33 4.2 7.0 3 or less 3.6 Com. Ex. 23 60 OR MORE 60 or more 8 60 or more Com. Ex. 24 7.8 9.1 3 or less 6.5 Com. Ex. 25 60 or more 60 or more 8 60 or more Com. Ex. 26 7.2 8.6 3 or less 5.9 The writing tool used was (1) an X-Y plotter (an aqueous ink) or (2)a brush pen (manufactured by Gochiku Seishydo Co., Ltd.) in case of "My Paper" (a trade name) and (3) an oily felt pen (manufactured by Mitsubishi Enpitsu Co., Ltd.) or (4)an aqueous felt pen (Mitsubishi Enpitsu Co., Ltd.). The X-Y plotter was "WX2400" (manufactured by Graphic Co., Ltd.) with a recording sheet speed of 1 cm/sec. and an input range of 0.5V. From Table 12 it will be seen that the samples in Examples 32 and 33 have greatly improved drying property when superimposition writing was made with a writing tool compared to the comparative examples, because the superfine silk fibroin particles was contained in the data display surface formation paint. On the other hand, it will be seen that the samples in Comparative Examples 23 to 26 do not have so satisfactory drying property when superimposition writing was made with a writing tool compared to Examples 32 and 33, because the superfine silk fibroin particles according to the invention was not contained or fine hydrophilic powder was used in lieu of the superfine silk fibroin particles. (4) Touch sense The touch sense was evaluated through evaluation of the overall character, test of writing and clarity of written letter by 20 randomly selected company monitors. The overall evaluation is the evaluation of the sense of touch to the coating film. The test of writing and clarity of written letter are evaluations concerning the writing accessibility. The evaluation standards were in five states from "5" (good" to "1" (bad). The results are shown in Table 13. Overall character Writing taste Clarity of written letter Example 32 5 5 4 Example 33 5 5 4 Com. Ex. 23 1 1 3 Com. Ex. 24 3 3 3 Com. Ex. 25 3 2 2 Com. Ex. 26 4 4 3 From Table 13, it will be seen that the samples in Examples 32 and 33 are satisfactory in all the characteristics of the overall character, writing taste and clarity of written letter, because the superfine silk fibroin particles according to the invention was contained in the data display surface formation paint. On the other hand. it will be seen that the samples in Comparative Examples 23 to 26 are unsatisfactory in at least one of the characters of the overall character, writing taste and clarity of written letter, because the superfine silk fibroin particles according to the invention was not contained or fine hydrophilic silica powder was contained in lieu of superfine silk fibroin particles. Industrial Utility The invention, owing to the incorporation of fine silk powder like fine natural organic material powder, is excellent in the moisture absorbing/releasing property, moisture permeability and touch sense, and is particularly suitable for application to plastic films and sheets, various moldings, paints, fiber treating materials, etc. which are frequently touched by the hand.

Claims: A method for producing silk fibroin ultrafine powder comprising: a first step for pulverizing silk fibroin into a crushed powder state by means of a dry-type mechanical pulverization means, a second step for pulverizing the silk fibroin crushed powder into a fine powder state by means of a dry-type mechanical pulverization means; a third step for pulverizing the silk fibroin fine powder into a ultrafine powder having average particle diameter on or less than 10µm by means of a dry-type mechanical pulverization means; and a step for beta-treating the silk fibroin powder in at least one step of the first to third steps or after the three steps. A method for producing silk fibroin ultrafine powder according to claim 1, wherein the dry-type mechanical pulverization means used in the second pulverizing step is a ball mill and wherein the dry-type mechanical pulverization means used in the third pulverising step is a jet mill. A method for producing silk fibroin ultrafine powder in accordance with either claim 1 or claim 2, wherein a liquid used in the beta treatment is a solvent medium or a neutral saline solution. Superfine silk fibroin particles manufactured by a process comprising a first commuting process for commuting silk fibroin into coarse particles with dry mechanical commuting means, a second commuting step of commuting the coarse silk fibroin particles into fine particles with dry mechanical commuting means, a third commuting means for commuting the fine silk fibroin particles into superfine particles with an average particle diameter of 10µm with dry mechanical commuting means, the silk fibroin particles being beta-treated during or after at least one of said first to third commuting steps. A solvent type resin composition obtained by incorporating the superfine silk fibroin particles according to claim 4 in a solvent type resin solution. A film or sheet containing superfine silk fibroin particles according to claim 4 in a solvent type resin solution. A laminate having a film or a sheet containing superfine silk fibroin particles according to claim 6 as one of a plurality of layers laminated on a base. A thermoplastic resin composition containing superfine silk fibroin particles obtained by incorporating the superfine silk fibroin particles according to claim 4 in a thermoplastic resin. A film or a sheet containing superfine silk fibroin particles obtained by incorporating the fine silk fibroin particles according to claim 4 in a thermoplastic resin. A laminate having a film or a sheet containing superfine silk fibroin particles according to claim 9 as one of a plurality of layers laminated on a base. A molding obtained by blow molding, hollow molding or press molding a thermoplastic resin composition containing superfine silk fibroin particles obtained by incorporating the superfine silk fibroin particles according to claim 4 in a thermoplastic resin. A composite molding comprising the molding according to claim 11 integral with a different article. A fiber treating material comprising a resin emulsion containing the superfine silk fibroin particles according to claim 4. A fiber treating material according to claim 13, wherein said resin emulsion comprises one or more members of the group consisting of polyurethane type resins, polyester type resins, silicon type resins, fluorine type resins and acrylic resins. Fibers, fiber material cloth or fiber material cotton treated with the fiber treating material according to claim 13 or 14. A paint containing superfine silk fibroin particles obtained by incorporating the superfine silk fibroin particles according to claim 4 in a resin. A paint containing superfine silk fibroin particles according to claim 16, wherein said resin is a solvent type resin. A paint containing superfine silk fibroin particles according to claim 16, wherein said resin is an aqueous resin. A data display surface formation paint obtained by incorporating the superfine silk fibroin particles according to claim 4 in a paint composition.

Inventors: FUKATSU FUMIOKI, MIKAMI SATOSHI, OHYAMA SHIGERU, SANO MASAHIRO, UBARA ATSUHIKO, YASUE TAKAHARU, FUKATSU, FUMIOKI, MIKAMI, SATOSHI, OHYAMA, SHIGERU, SANO, MASAHIRO, UBARA, ATSUHIKO, YASUE, TAKAHARU, Fukatsu, Fumioki Idemitsu Petrochem. Co., Ltd., Mikami, Satoshi, Idemitsu Petrochem. Co., Ltd., Ohyama, Shigeru, Idemitsu Petrochem. Co., Ltd., Sano, Masahiro, Idemitsu Petrochem. Co., Ltd., Ubara, Atsuhiko, Idemitsu Petrochem. Co., Ltd., Yasue, Takaharu, Idemitsu Petrochem. Co., Ltd.
Applicants: IDEMITSU PETROCHEMICAL CO, IDEMITSU PETROCHEMICAL CO. LTD.
Application year: 1994
Main classification: C08J5
IPC codes: B32B5, C08L89, C09D7, C08J3, C08L5, C08L1